Hair treatment compositions

ABSTRACT

This invention relates to an aqueous conditioner composition comprising (i) a cationic surfactant, (ii) a fatty alcohol material, and (iii) from 0.01 to 10 wt % coated particles comprising (a) a solid core having a D3,2 average particle size in the range from 10 to 700 nm, and (b) a coating of silicone polymer covalently bonded to the solid core. Use of the coated particles in a conditioner composition to impart body to the hair is also disclosed.

FIELD OF THE INVENTION

[0001] This invention relates to rinse-off hair conditioner compositionsand to their use in the treatment of hair.

BACKGROUND AND PRIOR ART

[0002] Shampoo compositions are generally formulated with highlyeffective cleansing surfactants, typically anionic surfactants, and donot in themselves provide much conditioning or styling benefit to thehair. In fact, basic shampoo formulations which have not beensupplemented with specific conditioning or styling agents have atendency to leave the hair in a cosmetically-unsatisfactory conditionwith regards to manageability and stylability. The hair tends to have aharsh, dull and dry feel, often referred to as “creak”, is oftendifficult to comb, in either the wet or the dry state, typically haspoor brushing properties, and tends to have poor set-retainingabilities.

[0003] This has resulted in the use of products containing specificconditioning and/or styling agents. Such agents are generally appliedseparately after shampooing and rinsing the hair, for example, in theform of conditioner formulations or styling mousses etc.

[0004] Conventional conditioner formulations, although providingsubstantial improvements in for example the wet and dry combingproperties of the hair and in the smoothness of the hair, do not inthemselves impart styling attributes such as body and volume to thehair. If fact, conventional conditioners tend to have a negative effecton many of the attributes associated with hair body.

[0005] One of the most common methods for imparting styling benefits tothe hair has been the use of hair fixative agents, such as highmolecular weight polymers. The problem with using such agents is thatthey have a tendency to negatively impact on conditioning attributessuch as wet and dry stage clean feel and smoothness. In fact, they canresult in a sticky feel to the hair.

[0006] Conventional styling polymers are typically water soluble. Thismeans that when incorporated into a conditioner which is rinsed off thehair, there is a tendency for the styling polymer to be washed away to agreater or lesser degree with the conditioner. Hence, most stylingproducts are leave-in products which are applied to the hair aspost-conditioner treatments.

[0007] The problem being addressed by the present invention is theprovision of rinse-off conditioner compositions which impart stylingbenefits, and in particular body benefits on the hair, but which do notnegatively impact on the conditioning benefits imparted by theconditioner. The body benefits or attributes the present invention islooking particularly to provide are root lift, increased hair volume,bounce, control (i.e. ease of styling) and manageability, i.e.maintenance of style without undue stiffness and negative sensory feel.Such body attributes are particularly attractive to people with fine orlong, weighty hair.

[0008] One approach that has been taken to address this problem has beenthe use different forms of styling agents such as small particulatematerials. Such an approach is described, for example, in ourunpublished PCT International Patent Application No. PCT/GB00/04020.This document describes the use of small hard particles, and inparticular colloidal silica, in hair treatment compositions to impartbody and volume to the hair. Although providing significant stylingbenefits, the use of these materials can still lead to small levels ofsensory negatives, such as for example a dry feel to the hair.

[0009] We have now found that the inclusion of a certain level of smallsolid particles covalently grafted with a silicone polymer inconventional conditioner formulations provides substantial stylingbenefits, in particular with regards to imparting body attributes to thehair. Furthermore, the conditioning attributes of conditionercompositions containing these particles are not compromised. Thecompositions are also stable.

[0010] JP 10144622 (Toshiba Silicone) discloses cosmetic compositionscontaining from 0.5 to 50 wt % of particles consisting of colloidalsilica cores surrounded by silicone shells which may be used on the skinor hair. Hairdressing lotions, hair creams and cleansing compositionssuch as a shampoo, rinse and conditioner are disclosed as suitablecosmetic compositions in which the particles can by utilised. In thetreatment of hair, they are described as providing a flexible and smoothfeeling and as having good set-retaining ability. There is no teachingthat the particles provide significant body benefits, such as volume,root lift and bounce, to the hair.

[0011] Although JP 10144622 discloses that the core-shell particles maybe used in a shampoo composition, only nonionic surfactants areidentified as being useful additional surfactant components when makingup cosmetic compositions comprising the particles. Nonionic surfactantsare also disclosed as improving the stability of the cosmeticcompositions. Anionic surfactants and cationic surfactants are discussedat length with respect to pre-emulsification of the particles, but thereis no mention of and no examples demonstrating the inclusion of suchsurfactants as additional components when making up the cosmeticcompositions. Example 13 in JP 10144622 describes a shampoo compositioncomprising 20 wt % nonionic surfactant, less than 0.01 wt % anionicsurfactant and more than 1 wt % core-shell particles.

[0012] We have found that the incorporation of the small particlescovalently grafted with silicone polymer into conventional conditionercompositions leads to substantive improvements in the body of theconditioned hair, especially if a subsequent styling regime is followed.The compositions impart body attributes, such as are root lift, volume,bounce and manageability, in the absence (or substantial absence) of astyling polymer, which leads to compositions which have a stylingbenefit, but nevertheless do not suffer from the sensory negatives (e.g.stickiness and/or dry feel) which are associated with prior stylingcompositions which are based on, for example, a styling polymer.

DEFINITION OF THE INVENTION

[0013] Accordingly, this invention provides an aqueous conditionercomposition comprising

[0014] (i) a cationic surfactant;

[0015] (ii) a fatty alcohol material; and

[0016] (iii) from 0.01 to 10 wt % of coated particles comprising

[0017] (a) a solid core having a D3,2 average particle size in the rangefrom 10 to 700 nm, and

[0018] (b) a coating of silicone polymer covalently bonded to the solidcore.

[0019] Additionally, this invention provides for use of coated particlesas defined above in a conditioner composition to impart body to hair.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

[0020] Definitions

[0021] Unless specified otherwise, all wt % values quoted hereinafterare percentages by weight based on total weight of the conditionercomposition.

[0022] As used hereinafter, the term “coated particle” refers to aparticle comprising a solid core having a D3,2 average particle size inthe range 10 to 700 nm which is coated, via covalent grafting, with asilicone polymer, the polymer forming a coating or shell around thesolid core.

[0023] As used hereinafter, the term “solid core” or “solid coreparticle” refers to the solid core of the coated particle.

[0024] As used hereinafter, the term “coating polymer” or “polymercoating” refers to the silicone polymer covalently grafted to the solidcore of the coated particle.

[0025] As used hereinafter, the term “water-insoluble”, means that thematerial is soluble in distilled water at a concentration of less than0.01 g/l, preferably less than 0.001 g/l at 20° C.

[0026] As used hereinafter, the term “aggregates” refers to secondaryparticles which are a collection of primary particles which have beenfused to form face to face sintered structures which cannot bedissociated, and as such are relatively hard.

[0027] D_(3,2) average droplet or particle sizes as referred to hereinmay be measured by means of a laser light scattering technique, using a2600D Particle Sizer from Malvern Instruments.

[0028] Coated Particles

[0029] The coated particles are present in the conditioner compositionin an amount of from 0.01 to 10, preferably from 0.01 to 5, morepreferably from 0.05 to 3, yet more preferably from 0.05 to 2.5, andmost preferably from 0.1 to 1 wt %. In particular, it has been foundthat levels of coated particles of 0.5 wt % or less work particularlywell in the compositions of the present invention.

[0030] The coated particles comprise solid cores having D3,2 averageparticle sizes in the range from 10 to 700 nm, the solid cores beingcoated with a silicone polymer which is covalently bonded to the solidcore.

[0031] Preferably, the D3,2 average particle size of the coatedparticles is in the range from 20 to 1000, more preferably from 20 to800, yet more preferably from 50 to 500 and most preferably from 50 to250 nm.

[0032] Sufficient silicone is grafted so as to form a effective shellaround the solid core. Suitably, the weight ratio of the solid core tothe silicone coating polymer is in the range from 20:1 to 1:10,preferably from 20:1 to 2:3, more preferably from 20:1 to 1:1, morepreferably from 10:1 to 1:1, yet more preferably from 5:1 to 1:1, andmost preferably from 5:1 to 2:1. A particularly preferred ratio is about4:1.

[0033] Although coated particles that are sparingly soluble may beemployed in conditioner compositions of the invention, it is highlypreferred that the coated particles be water-insoluble.

[0034] Solid Core

[0035] The solid core particles have a D3,2 average particle size in therange from 10 to 700, preferably from 10 to 500, more preferably from 20to 300, yet more preferably from 20 to 200, and most preferably from 30to 150 nm, for example about from 50 to 100 nm.

[0036] It is preferred that the solid core particles be colloidal in anaqueous dispersion.

[0037] The solid core can be a primary particle or an aggregate, so longas its satisfies the size requirement specified above. Preferably, it isa primary particle.

[0038] Suitably, the solid core particles are relatively hard andtypically have a Youngs Modulus of more than 0.01, preferably more than0.1, more preferably more than 1.0, yet more preferably more than 4 GPa,and yet more preferably more than 10 GPa.

[0039] The solid core material can be organic or inorganic in nature.Furthermore, the solid core may be composed entirely of one material ormay consist of a composite of materials.

[0040] Suitable organic solid particles can be made by a variety ofmethods including:

[0041] (i) via the synthesis of (co)polymers as described in, forexample, Breiner et al. (1998) Macromolecules, Vol. 31, 135; and

[0042] (ii) via the synthesis of cross-linked polymer structures asdescribed in, for example:

[0043] Ishizu & Fukutomi (1988) J. Polym. Sci., Part C: Polym. Lett.,Vol. 26, 281;

[0044] Saito et al. (1990) Polymer, Vol. 31, 679;

[0045] Thurmond et al. (1997) J. Am. Chem. Soc., Vol. 119, 6656; and

[0046] Stewart & Liu (2000) Agnew. Chem. Int. Ed., Vol. 39, 340).

[0047] Suitable inorganic solid particles can be prepared by techniquessuch as:

[0048] (i) precipitation, as described in, for example, Matjievic (1993)Chem. Mater., Vol. 5, 412;

[0049] (ii) dispersion, as described in, for example, Stober et al.(1968) J. Colloid Interface Sci., Vol. 26, 62; and Philipse & Vrij(1989) J. Colloid Interface Sci., Vol. 129, 121);

[0050] (iii) microemulsion processes, as described in, for example,Baumann et al. (1997) Adv. Mater., Vol. 9, 995; and

[0051] (iv) sol-gel processes, as described in, for example:

[0052] Forster & Antonietti (1998) Adv. Mater., Vol. 10, 195;

[0053] Kramer et al. (1998) Langmuir, Vol. 14, 2027;

[0054] Hedrick et al. (1998) Adv. Mater., Vol. 10, 1049;

[0055] Zhao et al. (1998) D. Science, Vol. 279, 548; and

[0056] Ulrich et al. (1999) Adv. Mater., Vol. 11, 141.

[0057] Examples of suitable solid core materials for use as the solidcores include polymers, which are preferably cross-linked, (e.g.polystyrene, silicone elastomer powders, PTFE, rubber), silicas,alumina, alumin silicate, clays and colloidal metals (e.g. titaniumdioxide, zinc oxide).

[0058] One preferred class of material is PTFE. PTFE solid coreparticles may be composed entirely of PTFE polymer or may consist of acomposite of PTFE polymer and one or more further polymers such aspolyethylene. Suitable PTFE particles are further described in ourunpublished copending United Kingdom Patent Application Nos. GB0012064.2 and GB 0012061.8.

[0059] Another preferred class of materials are silicas, such as silicagels, hydrated silicas and precipitated silicas (e.g. Cab-O-Sil andAerosil).

[0060] A particularly preferred class of solid core materials are thecolloidal silicas. Suitable examples include Ludox HS-40, Ludox SM,Ludox CL and Ludox AM.

[0061] Suitably, the solid core amounts to from 95 to 5 wt %, preferablyfrom 95 to 40, more preferably from 90 to 50, and most preferably from90 to 60 wt %, for example about 80 wt %, of the total weight of thecoated particles.

[0062] Solid cores that are either water-insoluble or only sparinglysoluble in water may be employed in the preparation of coated particles.Preferably, the solid core is water-insoluble.

[0063] Coating Polymer

[0064] The coating polymer is a silicone polymer which is covalentlybonded to the solid core.

[0065] Suitably, the coating polymer amounts to from 5 to 95, preferablyfrom 10 to 60, more preferably from 10 to 50, and most preferably from10 to 40 wt %, for example about 20 wt %, of the total weight of thecoated particles.

[0066] Suitably, the molecular weight of the coating polymer is nogreater than 500,000, preferably no greater than 250,000, morepreferably no greater than 200,000, yet more preferably no greater than150,000 and yet more preferably no greater than 100,000 Daltons. Themolecular weight may be lower than 50,000 or even lower than 25,000Daltons.

[0067] Suitably, the molecular weight is at least 500, preferably atleast 1,000, more preferably at least 2,000 and yet more preferably atleast 5,000 Daltons.

[0068] The silicone polymer is tethered to the surface of the solid coreparticle by one or more covalent bonds, although other secondary meansof attachment such as hydrogen bonding and absorption may also bepresent. The silicone polymer may be bonded via its terminal end(s)and/or via side-chains in the polymer chain. Preferably at least 70 wt%, more preferably at least 80 wt % and yet more preferably at least 90wt % of the silicone polymer present in coating on the solid core iscovalently bonded to the solid core surface.

[0069] More than one silicone polymer may be used to coat the solidcore.

[0070] Suitable silicone polymers for use as the coating polymer arepolyorganosiloxanes represented by the formula I:

R¹ _(a)SiO_((4-a)/2)   (I)

[0071] in which

[0072] R¹ is a hydrogen atom or a substituted or unsubstitutedhydrocarbon group; and

[0073] a is 1.80-2.20.

[0074] Examples of suitable unsubstituted hydrocarbon groups include (i)linear or branched C1-20 alkyls group; (ii) aryl groups such as benzyl,β-phenylethyl, methylbenzyl and naphthylmethyl groups; and (iii)cycloalkyl groups such as cyclohexyl and cyclopentyl.

[0075] Examples of suitable substituted hydrocarbon groups include (i)groups where hydrogen atom(s) of the above-mentioned unsubstitutedhydrocarbon groups is/are substituted with halogen atom(s) such asfluorine or chlorine, for example 3,3,3-trifluoropropyl and fluoropropylgroups; (ii) groups containing an ethylenic unsaturated group; and (iii)groups containing an organic functional group containing at least oneoxygen or nitrogen atoms.

[0076] Suitable organic functional groups include:

[0077] —CH₂CH₂CH₂NH₂

[0078] —CH₂CH₂CH₂NHCH₂CH₂NH₂

[0079] —CH₂CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂

[0080] Suitable ethylenic unsaturated groups include the following, inwhich n is an integer from 0 to 10:

[0081] (a) CH₂═CH—O—(CH₂)_(n)

[0082] suitable examples being vinyloxyethyl and vinyloxyethoxy groups,and preferably vinyloxypropyl and vinyloxyethoxypropyl groups;

[0083] (b) CH2═CH—(CH2)_(n)

[0084] suitable examples being homoallyl, 5-hexenyl and 7-octenylgroups, and preferably vinyl and allyl groups;

[0085] in which

[0086] R¹ is a hydrogen atom or a C1-6 alkyl group, preferably ahydrogen atom or methyl group.

[0087] Suitable examples include (vinylphenyl)methyl,isopropenylvinylphenyl, 2-(vinylphenoxy)ethyl,3-(vinylbenzoyloxy)propyl, 3-(isopropenylbenzoylkoxy)propyl, and3-(isopropenylbenzoyloxy)propyl groups. Preferred groups arevinylphenyl, 1-(vinylphenyl)ethyl and 2-(vinylphenyl)ethyl groups;

[0088] in which

[0089] R² is a C1-6 alkylene group or a group represented by the formula

—O—, S— or —N(R³)R⁴—

[0090] where

[0091] R³ is a C1-6 hydrocarbon or a (meth)acryloyl group, and

[0092] R⁴ is a C1-6 alkylene group.

[0093] Suitable examples include γ-acryloxypropyl, γ-methacrylaoxypropyland N,N-bis(methacryloyl)-γ-aminopropyl groups. Preferred groups areN-methacryloyl-N-methyl-γ-aminopropyl andN-acryloyl-N-methyl-γ-aminopropyl groups.

[0094] Preparation of Coated Particles

[0095] The coated particles are preferably prepared as an aqueouspre-emulsion, which can then be mixed with other ingredients to form theconditioner composition.

[0096] Different methods of preparation may be used depending of thesize of coated particles required. Suitably, the coated particles can beprepared as follow:

[0097] (i) “Large” Coated Particles

[0098] Larger coated particles, for example having a D3,2 averageparticle size of at least 100 nm and which employ solid core particleshaving D3,2 average particle size of at least 50 nm, can be prepared inan aqueous polymerisation system in which the solid core particles aremixed with water, an emulsifying surfactant, an organosiloxane componentand a suitable polymerisation catalyst. The resulting aqueous emulsionof coated particles can be directly incorporated into a conditionercomposition.

[0099] (ii) “Small” Coated Particles

[0100] Smaller coated particles, for example having a D3,2 averageparticle size of less than 100 nm and which employ solid core particleshaving D3,2 average particle size of less than 50 nm, tend to have to beprepared by an alternative organic polymerisation system in which thesolid core particles are mixed with an organosiloxane component in anorganic solvent, free of any surfactant. The resulting coated particlesare typically precipitated out of the organic solvent, washed andredispersed in water as an aqueous emulsion with a suitable emulsifyingsurfactant.

[0101] Organosiloxane Units

[0102] The silicone coating polymer is suitably prepared bypolymerisation of component monomers or oligomers. Typically, the solidcore particles are mixed with organosiloxane units having 2-10 siliconatoms and containing no hydroxyl groups and being of unit formula (II):

R¹ _(n)SiO_((4-n)/2)   (II)

[0103] in which

[0104] R¹ is a hydrogen atom or a substituted or unsubstitutedhydrocarbon group.

[0105] A cross-linking agent such as a silane compound having afunctional group may be added to the organosiloxane component for thesilicone coat so as to improve the strength of the polymer shell.

[0106] Examples of suitable organosiloxane component units from whichthe polyorganosiloxane coating polymer is formed by the condensationreaction are as follows:

[0107] (i) Cyclic compounds such as hexamethyl cyclotrisiloxane,octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane,1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl cyclotetrasiloxane,1,3,5,7-tetrabenzyltetramethyl cyclotetrasiloxane and1,3,5,7-tris(3,3,3-trifluoropropyl)trimethylsiloxane;

[0108] (ii) Cyclic organosiloxanes containing an organic functionalgroup such as trimethyl triphenyl cyclotrisiloxane,tris(3,3,3-aminopropyl) tetramethyl cyclotetrasiloxane,1,3,5,7-tetra[N-(2-aminoethyl)-3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7,-tetra(3-mercaptopropyl) tetramethylcyclotetrasiloxane and 1,3,5,7,-tetra(3glycidoxypropyl) tetramethylcyclotetrasiloxane.

[0109] (iii) Cyclic and linear organosiloxanes having an ethylenicallyunsaturated group such as 1,3,5,7-tetra(3-methacryloxypropyl)tetramethyl cyclotetrasiloxane, 1,3,5,7-tetra(3-acryloxypropyl)tetramethyl cyclotetrasiloxane, 1,3,5,7-tetra(3-carboxypropyl)tetramethyl cyclotetrasiloxane, 1,3,5,7-tetra(vinyloxypropyl)tetramethyl cyclotetrasiloxane, 1,3,5,7,-tetra(vinyloxyethoxypropyl)tetramethyl tetracyclosiloxane, 1,3,5,7-tetra(p-vinylphenyl) tetramethylcyclotetrasiloxane, 1,3,5,7,-tetra[1-(m-vinylphenyl)methyl] tetramethylcyclotetrasiloxane, 1,3,5,7,-tetra[2(p-vinylphenyl)ethyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra[3-(p-vinylphenoxy)propyl] tetramethylcyclotetrasiloxane, 1,3,5,7,-tetra[3-(p-vinylbenzoyloxy)propyltetramethyl tetracyclosilaoxane,1,3,5,7,-tetrea[3-(p-isopropenylbenzoylamino)propyl] tetramethyltetracyclosiloxane,1,3,5,7,-tetra(N-methacryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7,-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethyl cyclotetrasiloxane,1,3,5,7,-tetra[N,N-bis(methacryloyl)-3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra[N,N-bis(acryloyl)-3-aminopropyl]tetramethyl cyclotetrasiloxane, 1,3,5,7-tetravinyl tetramethylcyclotetrasiloxane, octavinyl cyclotetrasiloxane, 1,3,5-trivinyltrimethyl cyclotrisiloxane, 1,3,5,7-tetraallyl tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(5-hexenyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(7-oxenyl) tetramethylcyclotetrasiloxane and 1-(p-vinylphenyl)-1,1-diphenyl-3-diethoxydisiloxane.

[0110] Examples of suitable silane compounds which may be added to theorganosiloxane component for the silicone coat so as to improve thestrength of the polymer shell are as follows:

[0111] (i) Silane compounds having an organic functional group such as3-aminopropylmethyl dimethoxysilane, 3-aminopropyltrimethoxysilane,N-(2-aminoethyl-3-aminopropyl trimethoxysilane,N-triethylenediaminepropylmethyl dimethoxysilane,3-glycidoxypropylmethyl dimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3-mercaptopropyl trimethoxysilane, trifluoropropyltrimethoxysilane and 3-carboxypropylmethyl dimethoxysilane.

[0112] (ii) Silane compounds having an ethylenic unsaturated group suchas 3-acryloxypropyl triethoxysilane, 3-methacryloxypropyltrimethoxysilane, (vinyloxypropyl)methyl dimethoxysilane,(vinyloxyethoxypropyl)methyl dimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1-(m-vinylphenyl)methyldimethyl isopropoxysilane,2-(p-vinylphenyl)ethyldimethoxysilane, 3-(p-vinylphenoxy)propylmethyldimethoxysilane, 1-(p-vinylphenyl)ethylmethyl methoxysilane,1-(o-vinylphenyl)-1,1,2-trimethyldimethoxydisilane,m-vinylphenyl[(3-triethoxysilyl)propl] diphenylsilane,[3-(p-isopropenylbenzoylamino)propyl] diphenyldipropoxysilane,N-methacryloyyl-N-methyl-3-aminopropylmethyl dimethoxysilane,N-acryloyl-N-methyl-3-aminopropylmethyl dimethoxysilane,N,N-bis(methacryloyl)-3-aminopropyl methoxysilane,N,N-bis(acryloyl)-3-aminopropylmethyl dimethoxysilane,N-methacryloyl-N-methyl-3-aminopropylphenyl diethoxysilane,1-methacryloylpropyl01,1,3-trimethyl-3,3-dimethoxydisiloxane,vinylmethyl dimethoxysilane, vinylethyl diisoproposysilane, allylmethyldimethoxysilane, 5-hexenylmethyl diethoxysilane and 3-octenylethyldiethoxysilane.

[0113] Any of the organosiloxanes or silanes can be used either singlyor as a mixture of two or more organosiloxanes and/or silanes.

[0114] Besides the above-mentioned silicones, linear or branchedorganosiloxane oligomers may also be used as an organosiloxanecontaining an organic functional group or an ethylenic unsaturatedgroup. In the case of such organosiloxane oligomers, although there isno particular limitation for the terminal group of the molecular chainterminal is sequestered by an organic group other than a hydroxyl groupsuch as an alkoxy group, trimethylsilyl group, dimethylvinylsilyl group,methylphenylvinylsilyl group, methyldiphenylsilyl group and3,3,3-trifluoropropyldimethylsilyl group.

[0115] Emulsifying Surfactant

[0116] Any surfactant materials either alone or in admixture may be usedas emulsifiers in the preparation of the pre-emulsions of coatedparticles. Suitable emulsifiers include anionic, cationic and nonionicemulsifiers.

[0117] Examples of anionic emulsifiers are alkylarylsulphonates, e.g.,sodium dodecylbenzene sulphonate, alkyl sulphates e.g., sodium, laurylsulphate, alkyl ether sulphates, e.g., sodium lauryl ether sulphate nEO,where n is from 1 to 20 alkylphenol ether sulphates, e.g., octylphenolether sulphate nEO where n is from 1 to 20, and sulphosuccinates, e.g.,sodium dioctylsulphosuccinate.

[0118] Suitable cationic surfactants are well-known to the personskilled in the art. Preferably, the cationic surfactant contains aquaternary ammonium group. Suitable examples of such cationicsurfactants are described hereinbelow in the section on co-surfactants.Particularly preferred as cationic emulsifying surfactants are C6-20,preferably C8-18, monoalkyl and dialkyl quaternary ammonium compounds.

[0119] Examples of nonionic emulsifiers are alkylphenol ethoxylates,e.g., nonylphenol ethoxylate nEO, where n is from 1 to 50, alcoholethoxylates, e.g., lauryl alcohol nEO, where n is from 1 to 50, esterethoxylates, e.g., polyoxyethylene monostearate where the number ofoxyethylene units is from 1 to 30.

[0120] Preferably, at least one anionic surfactant or cationicsurfactant is present as an emulsifying surfactant.

[0121] (i) Aqueous Polymerisation System

[0122] In this process, the solid core particles are mixed with water,an emulsifying surfactant, an organosiloxane component and a suitablepolymerisation catalyst. Preferred methods for preparing coatedparticles according to this system are described in JP 10114622.

[0123] Any catalyst may be used so long as it is capable of polymerisinga low-molecular organosiloxane in the presence of water. Suitablecatalysts include those commonly used for polymerisation oflow-molecular organosiloxanes such as a mixture of hydroxylatedaliphatic sulphonic acid with an unsaturated aliphatic sulphonic acid,an aliphatic hydrogen sulphate, an aliphatic substitutedbenzenesulphonic acid, hydrochloric acid, sulphuric acid, phosphoricacid.

[0124] Certain anionic surfactant emulsifiers have a weak catalyticaction such can be used in conjunction with a polymerisation catalyst.Such anionic surfactants include sodium dodecylbenzenesulphonate, sodiumoctylbenzenesulphonate, ammonium dodecylbenzenesulphonate, sodium laurylsulphate, ammonium lauryl sulphate, triethanolamine lauryl sulphate,sodium tetradecenesulphonate and sodium hydroxytetradecenesulphonate.

[0125] Cationic surfactant emulsifiers can also have a weak catalyticaction and, therefore, it is preferred to use them together with apolymerization catalyst such as an alkaline metal hydroxide (e.g.,lithium hydroxide, sodium hydroxide, potassium hydroxide, potassiumhydroxide, rubidium hydroxide and caesium hydroxide).

[0126] The amount of water used in the emulsification is typically from50 to 500, preferably from 100 to 300 parts by weight to 100 parts byweight of the total amount of the coated particles component in theemulsion. The solid concentration in the emulsion is typically from 20to 70, preferably from 30 to 60 wt % of the total weight of theemulsion. The temperature of preparation of the emulsion (i.e. for thecondensation reaction) is typically in the range from 5 to 100° C.

[0127] The amount of emulsifying surfactant in the emulsification istypically from 0.5 to 50, preferably from 0.5 to 20 parts by weight ofthe total amount of the coated particles component in the emulsion.

[0128] The amount of polymerization catalyst in the emulsification istypically from 0.05 to 10 parts by weight of the total amount of thecoated particles component in the emulsion.

[0129] As already mentioned, a preferred solid core material of thepresent invention is colloidal silica. In the emulsification step, thisis present as an aqueous dispersion with SiO₂ as the basic unit of thesolid core particles. Ordinarily, colloidal silica is classified intoacidic and alkaline subclasses based upon its characteristics and any ofthem may be appropriately selected and used depending upon the conditionfor the emulsification polymerisation. When using acidic silica, theemulsifying surfactant should be an anionic surfactant, and conversely,when using an alkaline silica, the emulsifying surfactant should be acationic surfactant, in order to keep the silica in a stable state.

[0130] In a preferred embodiment, the emulsifying surfactant is ancationic surfactant. Thus when using silica as the solid core,preferably alkaline silica is used. The coated particle emulsionprepared using cationic surfactant as the emulsifying agent has beenfound to produce conditioner formulations which are more stable.

[0131] (ii) Organic Polymerisation System

[0132] In this process, the solid core particles are mixed with anorganosiloxane component in an organic solvent, free of any surfactant.The resulting coated particles are typically precipitated out of theorganic solvent, washed and redispersed in water with a suitableemulsifying surfactant to form an aqueous emulsion. Preferred methodsfor preparing coated particles according to this system are described inPyun et al. (2001) Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.),Vol. 42(1), 223.

[0133] A suitable method for preparing “smaller” coated particles, forexample in which the solid core particles have a D3,2 average particlesize of 10 to 20 nm. is a microemulsion process. An example of asuitable microemulsion process for the preparation of silica solid corescoated with silicone polymer is as follows. Silica colloid is preparedin an aqueous medium (e.g. 6 mM NaOH) by the reaction ofmethyltrimethoxysilane within micelles in the presence of an emulsifyingsurfactant (e.g. a quaternary ammonium cationic surfactant). Thepresence of the surfactant around the particles prevents large-scaleflocculation. In order to prevent the colloid particles aggregating viaresidual surface silanol groups, the surface silanol groups of thesilica colloid are silylised. Firstly, whilst still in the aqueousmedium, surface silanol groups are reacted with methoxytrimethylsilaneto generate trimethylsilyl groups. The particles are then precipitatedinto an appropriate organic solvent (e.g. methanol) to remove thesurfactant, and subsequently redispersed in an appropriate organicsolvent (e.g. tetrahydofurnan). The transfer from aqueous to organicsolvent is necessary to achieve complete silylisation of the surfacesilanol groups and thus obtain stable colloids. Any residual silanolgroups are deactivated and 2-bromoisobutyrate groups incorporated ontothe surface of the particles by reacting the colloid particles in anappropriate organic solvent with3-(2-bromoisobutyryloxy)-propylchlorodimethylsilane and1,1,1,3,3,-hexamethyldisilazane. The functionalised silica colloids canthen be purified by precipitation, e.g. in methanol, and dialysis inacetone. The functionalised silica colloids are then coated by reactionwith organosiloxane units in an atom transfer radical polymerisation(ATRP) to form coated particles.

[0134] The coated particles are finally precipitated out of the organicsolvent, for example, into methanol, washed (e.g. with acetone) andredispersed in water with a suitable emulsifying surfactant to form anaqueous pre-emulsion of coated particles.

[0135] Preferably, whatever method of preparation is used, theemulsifying surfactant present in the aqueous pre-emulsion of coatedparticles is a cationic surfactant.

[0136] The pre-emulsions of the coated particles have a tendency to beeither acidic or alkaline in nature. In order to keep them stable over along period, they are neutralised by adding alkali or acid. Examples ofsuitable alkali neutralising agents are sodium hydroxide, thoriumcarbonate, thorium bicarbonate and triethanolamine. Examples of suitableacidic neutralising agents are hydrochloric acid, sulphuric acid, nitricacid, acetic acid and oxalic acid.

[0137] Conditioner Compositions

[0138] Compositions of the invention are formulated as conditioners forthe treatment of hair (typically after shampooing) and subsequentrinsing.

[0139] Conditioning Surfactant

[0140] The conditioner compositions of the present invention compriseone or more conditioning surfactants which are cosmetically acceptableand suitable for topical application to the hair.

[0141] Suitable conditioning surfactants are selected from cationicsurfactants, used singly or in admixture.

[0142] Cationic surfactants useful in compositions of the inventioncontain amino or quaternary ammonium hydrophilic moieties which arepositively charged when dissolved in the aqueous composition of thepresent invention.

[0143] Examples of suitable cationic surfactants are those correspondingto the general formula:

[N(R₁) (R₂) (R₃) (R₄)]⁺ (X)⁻

[0144] in which R₁, R₂, R₃, and R₄ are independently selected from (a)an aliphatic group of from 1 to 22 carbon atoms, or (b) an aromatic,alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylarylgroup having up to 22 carbon atoms; and X is a salt-forming anion suchas those selected from halogen, (e.g. chloride, bromide), acetate,citrate, lactate, glycolate, phosphate nitrate, sulphate, andalkylsulphate radicals.

[0145] The aliphatic groups can contain, in addition to carbon andhydrogen atoms, ether linkages, and other groups such as amino groups.The longer chain aliphatic groups, e.g., those of about 12 carbons, orhigher, can be saturated or unsaturated.

[0146] The most preferred cationic surfactants for conditionercompositions of the present invention are monoalkyl quaternary ammoniumcompounds in which the alkyl chain length is C8 to C14.

[0147] Suitable examples of such materials correspond to the generalformula:

[N(R₅) (R₆) (R₇) (R₈)]⁺ (X)⁻

[0148] in which R₅ is a hydrocarbyl chain having 8 to 14 carbon atoms ora functionalised hydrocarbyl chain with 8 to 14 carbon atoms andcontaining ether, ester, amido or amino moieties present as substituentsor as linkages in the radical chain, and R₆, R₇ and R₈ are independentlyselected from (a) hydrocarbyl chains of from 1 to about 4 carbon atoms,or (b) functionalised hydrocarbyl chains having from 1 to about 4 carbonatoms and containing one or more aromatic, ether, ester, amido or aminomoieties present as substituents or as linkages in the radical chain,and X is a salt-forming anion such as those selected from halogen, (e.g.chloride, bromide), acetate, citrate, lactate, glycolate, phosphatenitrate, sulphate, and alkylsulphate radicals.

[0149] The functionalised hydrocarbyl chains (b) may suitably containone or more hydrophilic moieties selected from alkoxy (preferably C₁-C₃alkoxy), polyoxyalkylene (preferably C₁-C₃ polyoxyalkylene), alkylamido,hydroxyalkyl, alkylester, and combinations thereof.

[0150] Preferably the hydrocarbyl chains R₁ have 12 to 14 carbon atoms,most preferably 12 carbon atoms. They may be derived from source oilswhich contain substantial amounts of fatty acids having the desiredhydrocarbyl chain length. For example, the fatty acids from palm kerneloil or coconut oil can be used as a source of C8 to C12 hydrocarbylchains.

[0151] Typical monoalkyl quaternary ammonium compounds of the abovegeneral formula for use in shampoo compositions of the inventioninclude:

[0152] (i) lauryl trimethylammonium chloride (available commercially asArquad C35 ex-Akzo); cocodimethyl benzyl ammonium chloride (availablecommercially as Arquad DMCB-80 ex-Akzo)

[0153] (ii) compounds of the general formula:

[N(R₁) (R₂) ((CH₂ CH₂ O)_(x) H) ((CH₂ CH₂ O)_(y) H)]^(+ (X)) ⁻

[0154] in which:

[0155] x+y is an integer from 2 to 20;

[0156] R₁ is a hydrocarbyl chain having 8 to 14, preferably 12 to 14,most preferably 12 carbon atoms or a functionalised hydrocarbyl chainwith 8 to 14, preferably 12 to 14, most preferably 12 carbon atoms andcontaining ether, ester, amido or amino moieties present as substituentsor as linkages in the radical chain;

[0157] R₂ is a C₁-C₃ alkyl group or benzyl group, preferably methyl, and

[0158] X is a salt-forming anion such as those selected from halogen,(e.g. chloride, bromide), acetate, citrate, lactate, glycolate,phosphate nitrate, sulphate, methosulphate and alkylsulphate radicals.

[0159] Suitable examples are PEG-n lauryl ammonium chlorides (where n isthe PEG chain length), such as PEG-2 cocomonium chloride (availablecommercially as Ethoquad C12 ex-Akzo Nobel); PEG-2 cocobenzyl ammoniumchloride (available commercially as Ethoquad CB/12 ex-Akzo Nobel); PEG-5cocomonium methosulphate (available commercially as Rewoquat CPEMex-Rewo); PEG-15 cocomonium chloride (available commercially as EthoquadC/25 ex-Akzo); PEG-2 oleamonium chloride (available commercially asEthoquad O/12 PG ex Akzo Nobel).

[0160] (iii) compounds of the general formula:

(N(R₁) (R₂) (R₃ ) ((CH₂)_(n) OH)]^(+ (X)) ⁻

[0161] in which:

[0162] n is an integer from 1 to 4, preferably 2;

[0163] R₁ is a hydrocarbyl chain having 8 to 14, preferably 12 to 14,most preferably 12 carbon atoms;

[0164] R₂ and R₃ are independently selected from C₁-C₃ alkyl groups, andare preferably methyl, and

[0165] X is a salt-forming anion such as those selected from halogen,(e.g. chloride, bromide), acetate, citrate, lactate, glycolate,phosphate nitrate, sulphate, and alkylsulphate radicals.

[0166] Suitable examples are lauryldimethylhydroxyethylammonium chloride(available commercially as Prapagen HY ex-Clariant)

[0167] Mixtures of any of the foregoing cationic surfactants compoundsmay also be suitable.

[0168] Examples of suitable cationic surfactants include:

[0169] quaternary ammonium chlorides, e.g. alkyltrimethylammoniumchlorides wherein the alkyl group has from about 8 to 22 carbon atoms,for example octyltrimethylammonium chloride, dodecyltrimethylammoniumchloride, hexadecyltrimethylammonium chloride, cetyltrimethylammoniumchloride, octyldimethylbenzylammonium chloride,decyldimethylbenzylammonium chloride, stearyldimethylbenzylammoniumchloride, didodecyldimethylammonium chloride,dioctadecyldimethylammonium chloride, tallow trimethylammonium chloride,cocotrimethylammonium chloride, and the corresponding salts thereof,e.g., bromides, hydroxides. Cetylpyridinium chloride or salts thereof,e.g., chloride

[0170] Quaternium -5

[0171] Quaternium -31

[0172] Quaternium -18

[0173] and mixtures thereof.

[0174] In the conditioners of the invention, the level of cationicsurfactant is preferably from 0.01 to 10, more preferably 0.05 to 5,most preferably 0.1 to 2 wt % of the total composition.

[0175] Fatty Alcohol Material

[0176] The conditioner compositions of the invention additionallycomprise a fatty alcohol material. The combined use of fatty alcoholmaterials and cationic surfactants in conditioning compositions isbelieved to be especially advantageous, because this leads to theformation of a lamellar phase, in which the cationic surfactant isdispersed.

[0177] By “fatty alcohol material” is meant a fatty alcohol, analkoxylated fatty alcohol, or a mixture thereof.

[0178] Representative fatty alcohols comprise from 8 to 22 carbon atoms,more preferably 16 to 20. Examples of suitable fatty alcohols includecetyl alcohol, stearyl alcohol and mixtures thereof. The use of thesematerials is also advantageous in that they contribute to the overallconditioning properties of compositions of the invention.

[0179] Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcoholshaving from about 12 to about 18 carbon atoms in the alkyl chain can beused in place of, or in addition to, the fatty alcohols themselves.Suitable examples include ethylene glycol cetyl ether, polyoxyethylene(2) stearyl ether, polyoxyethylene (4) cetyl ether, and mixturesthereof.

[0180] The level of fatty alcohol material in conditioners of theinvention is suitably from 0.01 to 15, preferably from 0.1 to 10, andmore preferably from 0.1 to 5 wt %. The weight ratio of cationicsurfactant to fatty alcohol is suitably from 10:1 to 1:10, preferablyfrom 4:1 to 1:8, optimally from 1:1 to 1:7, for example 1:3.

[0181] Optional Ingredients

[0182] Compositions of this invention may contain any other ingredientsnormally used in conditioner formulations. These other ingredients mayinclude additional conditioning agents, viscosity modifiers, suspendingagents, preservatives, colouring agents, polyols such as glycerine andpolypropylene glycol, chelating agents such as EDTA, antioxidants,fragrances, antimicrobials and sunscreens. Each of these ingredientswill be present in an amount effective to accomplish its purpose.Generally these optional ingredients are included individually at alevel of up to 5 wt % of the total composition.

[0183] Cationic Polymers

[0184] The compositions according to the present invention may comprisea cationic polymer for enhancing conditioning performance of theconditioner.

[0185] The cationic polymer may be a homopolymer or be formed from twoor more types of monomers. The molecular weight of the polymer willgenerally be between 5 000 and 10 000 000, typically at least 10 000 andpreferably in the range 100 000 to about 2 000 000. The polymers willhave cationic nitrogen containing groups such as quaternary ammonium orprotonated amino groups, or a mixture thereof.

[0186] The cationic nitrogen-containing group will generally be presentas a substituent on a fraction of the total monomer units of thecationic polymer. Thus when the polymer is not a homopolymer it cancontain spacer non-cationic monomer units. Such polymers are describedin the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of thecationic to non-cationic monomer units is selected to give a polymerhaving a cationic charge density in the required range.

[0187] Suitable cationic conditioning polymers include, for example,copolymers of vinyl monomers having cationic amine or quaternaryammonium functionalities with water soluble spacer monomers such as(meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl(meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl anddialkyl substituted monomers preferably have C1-C7 alkyl groups, morepreferably C1-3 alkyl groups. Other suitable spacers include vinylesters, vinyl alcohol, maleic anhydride, propylene glycol and ethyleneglycol.

[0188] The cationic amines can be primary, secondary or tertiary amines,depending upon the particular species and the pH of the composition. Ingeneral secondary and tertiary amines, especially tertiary, arepreferred.

[0189] Amine substituted vinyl monomers and amines can be polymerized inthe amine form and then converted to ammonium by quaternization.

[0190] The cationic conditioning polymers can comprise mixtures ofmonomer units derived from amine- and/or quaternary ammonium-substitutedmonomer and/or compatible spacer monomers.

[0191] Suitable cationic conditioning polymers include, for example:

[0192] copolymers of 1-vinyl-2-pyrrolidine and1-vinyl-3-methyl-imidazolium salt (e.g. chloride salt), referred to inthe industry by the Cosmetic, Toiletry, and Fragrance Association,(CTFA) as Polyquaternium-16. This material is commercially availablefrom BASF Wyandotte Corp. (Parsippany, N.J., USA) under the LUVIQUATtradename (e.g. LUVIQUAT FC 370);

[0193] copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethylmethacrylate, referred to in the industry (CTFA) as Polyquaternium-11.This material is available commercially from Gaf Corporation (Wayne,N.J., USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N);

[0194] cationic diallyl quaternary ammonium-containing polymersincluding, for example, dimethyldiallyammonium chloride homopolymer andcopolymers of acrylamide and dimethyldiallylammonium chloride, referredto in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7,respectively;

[0195] mineral acid salts of amino-alkyl esters of homo-and co-polymersof unsaturated carboxylic acids having from 3 to 5 carbon atoms, (asdescribed in U.S. Pat. No. 4,009,256);

[0196] cationic polyacrylamides(as described in WO95/22311).

[0197] Other cationic conditioning polymers that can be used includecationic polysaccharide polymers, such as cationic cellulosederivatives, cationic starch derivatives, and cationic guar gumderivatives. Suitably, such cationic polysaccharide polymers have acharge density in the range from 0.1 to 4 meq/g.

[0198] Cationic polysaccharide polymers suitable for use in compositionsof the invention include those of the formula:

A—O—[R—N⁺ (R¹) (R²) (R³)X^(−],)

[0199] wherein: A is an anhydroglucose residual group, such as a starchor cellulose anhydroglucose residual. R is an alkylene, oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R¹,R² and R³ independently represent alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms. The total number of carbon atoms for each cationic moiety(i.e., the sum of carbon atoms in R¹, R² and R³) is preferably about 20or less, and X is an anionic counterion.

[0200] Cationic cellulose is available from Amerchol Corp. (Edison,N.J., USA) in their Polymer JR (trade mark) and LR (trade mark) seriesof polymers, as salts of hydroxyethyl cellulose reacted with trimethylammonium substituted epoxide, referred to in the industry (CTFA) asPolyquaternium 10. Another type of cationic cellulose includes thepolymeric quaternary ammonium salts of hydroxyethyl cellulose reactedwith lauryl dimethyl ammonium-substituted epoxide, referred to in theindustry (CTFA) as Polyquaternium 24. These materials are available fromAmerchol Corp. (Edison, N.J., USA) under the tradename Polymer LM-200.

[0201] Other suitable cationic polysaccharide polymers includequaternary nitrogen-containing cellulose ethers (e.g. as described inU.S. Pat. No. 3,962,418), and copolymers of etherified cellulose andstarch (e.g. as described in U.S. Pat. No. 3,958,581).

[0202] A particularly suitable type of cationic polysaccharide polymerthat can be used is a cationic guar gum derivative, such as guarhydroxypropyltrimonium chloride (commercially available fromRhone-Poulenc in their JAGUAR trademark series).

[0203] Examples are JAGUAR C13S, which has a low degree of substitutionof the cationic groups and high viscosity. JAGUAR C15, having a moderatedegree of substitution and a low viscosity, JAGUAR C17 (high degree ofsubstitution, high viscosity), JAGUAR C16, which is a hydroxypropylatedcationic guar derivative containing a low level of substituent groups aswell as cationic quaternary ammonium groups, and JAGUAR 162 which is ahigh transparency, medium viscosity guar having a low degree ofsubstitution.

[0204] Preferably the cationic conditioning polymer is selected fromcationic cellulose and cationic guar derivatives. Particularly preferredcationic polymers are JAGUAR C13S, JAGUAR C15, JAGUAR C17 and JAGUAR C16and JAGUAR C162.

[0205] The cationic conditioning polymer will generally be present incompositions of the invention at levels of from 0.01 to 5, preferablyfrom 0.05 to 1, more preferably from 0.08 to 0.5 wt %.

[0206] Conditioning Agents

[0207] The compositions of the present invention may also contain one ormore additional conditioning agents selected from silicone conditioningagents and non-silicone oily conditioning agents.

[0208] When conditioning agent is present in the compositions of thepresent invention in droplet form, the droplets may be liquid,semi-solid or solid in nature, so long as they are substantiallyuniformly dispersed in the fully formulated product. Any droplets ofoily conditioning agent are preferably present as either liquid orsemi-solid droplets, more preferably as liquid droplets.

[0209] Silicone Conditioning Agents

[0210] The compositions of the invention may contain emulsified dropletsof a silicone conditioning agent for enhancing conditioning performance.The silicone is insoluble in the aqueous matrix of the composition andso is present in an emulsified form, with the silicone present asdispersed droplets.

[0211] Suitable silicones include polydiorganosiloxanes, in particularpolydimethylsiloxanes which have the CTFA designation dimethicone. Alsosuitable for use compositions of the invention (particularly shampoosand conditioners) are polydimethyl siloxanes having hydroxyl end groups,which have the CTFA designation dimethiconol. Also suitable for use incompositions of the invention are silicone gums having a slight degreeof cross-linking, as are described for example in WO 96/31188. Thesematerials can impart body, volume and stylability to hair, as well asgood wet and dry conditioning.

[0212] The viscosity of the emulsified silicone itself (not the emulsionor the final hair conditioning composition) is typically at least 10,000cst. In general we have found that conditioning performance increaseswith increased viscosity. Accordingly, the viscosity of the siliconeitself is preferably at least 60,000 cst, most preferably at least500,000 cst, ideally at least 1,000,000 cst. Preferably the viscositydoes not exceed 10⁹ cst for ease of formulation.

[0213] Emulsified silicones for use in the shampoo compositions of theinvention will typically have an average silicone droplet size in thecomposition of less than 30, preferably less than 20, more preferablyless than 10 μm. We have found that reducing the droplet size generallyimproves conditioning performance. Most preferably the average siliconedroplet size of the emulsified silicone in the composition is less than2 μm, ideally it ranges from 0.01 to 1 μm. Silicone emulsions having anaverage silicone droplet size of ≦0.15 μm are generally termedmicroemulsions.

[0214] Suitable silicone emulsions for use in the invention are alsocommercially available in a pre-emulsified form.

[0215] Examples of suitable pre-formed emulsions include emulsionsDC2-1766, DC2-1784, and microemulsions DC2-1865 and DC2-1870, allavailable from Dow Corning. These are all emulsions/microemulsions ofdimethiconol. Cross-linked silicone gums are also available in apre-emulsified form, which is advantageous for ease of formulation. Apreferred example is the material available from Dow Corning as DCX2-1787, which is an emulsion of cross-linked dimethiconol gum. Afurther preferred example is the material available from Dow Corning asDC X2-1391, which is a microemulsion of cross-linked dimethiconol gum.

[0216] A further preferred class of silicones for inclusion in shampoosand conditioners of the invention are amino functional silicones. By“amino functional silicone” is meant a silicone containing at least oneprimary, secondary or tertiary amine group, or a quaternary ammoniumgroup.

[0217] Examples of suitable amino functional silicones include:

[0218] (i) polysiloxanes having the CTFA designation “amodimethicone”,and the general formula:

HO—[Si(CH₃)₂—O—]_(x)—[Si(OH) (CH₂CH₂CH₂—NH—CH₂CH₂NH₂)—O—]_(y)—H

[0219] in which x and y are numbers depending on the molecular weight ofthe polymer, generally such that the molecular weight is between about5,000 and 500,000.

[0220] (ii) polysiloxanes having the general formula:

R′_(a)G_(3-a)—Si (OSiG₂)_(n)—(OSiG_(b)R′_(2-b))_(m)—O—SiG_(3-a)—R′_(a)

[0221] in which:

[0222] G is selected from H, phenyl, OH or C₁₋₈ alkyl, e.g. methyl;

[0223] a is 0 or an integer from 1 to 3, preferably 0;

[0224] b is 0 or 1, preferably 1;

[0225] m and n are numbers such that (m+n) can range from 1 to 2000,preferably from 50 to 150;

[0226] m is a number from 1 to 2000, preferably from 1 to 10;

[0227] n is a number from 0 to 1999, preferably from 49 to 149, and

[0228] R′ is a monovalent radical of formula —C_(q)H_(2q)L in which q isa number from 2 to 8 and L is an aminofuctional group selected from thefollowing:

[0229] —NR″—CH₂—CH₂—N(R″)₂

[0230] —N(R″)₂

[0231] —N⁺(R″)₃A⁻

[0232] —N⁺H(R″)₂ A⁻

[0233] —N⁺H₂(R″) A⁻

[0234] —N(R″)—CH₂—CH₂—N⁺H₂(R″) A⁻

[0235] in which R″ is selected from H, phenyl, benzyl, or a saturatedmonovalent hydrocarbon radical, e.g. C₁₋₂₀ alkyl, and A is a halide ion,e.g. chloride or bromide.

[0236] Suitable amino functional silicones corresponding to the aboveformula include those polysiloxanes termed“trimethylsilylamodimethicone” as depicted below, and which aresufficiently water insoluble so as to be useful in compositions of theinvention:

Si(CH₃)₃—O—[Si(CH₃)₂—O—]_(x)—[Si (CH₃) (R—NH—CH₂CH₂ NH₂)—O—]_(y)—Si(CH₃)₃

[0237] wherein x+y is a number from about 50 to about 500, and wherein Ris an alkylene group having from 2 to 5 carbon atoms. Preferably, thenumber x+y is in the range of from about 100 to about 300.

[0238] (iii) quaternary silicone polymers having the general formula:

{(R¹) (R²) (R³) N⁺ CH₂CH(OH)CH₂O(CH₂)₃[Si (R⁴) (R⁵)—O—]_(n)—Si (R⁶)(R⁷)—(CH₂)₃—O—CH₂CH(OH)CH₂N⁺ (R⁸) (R⁹) (R¹⁰)} (X⁻⁾ ₂

[0239] wherein R¹ and R¹⁰ may be the same or different and may beindependently selected from H, saturated or unsaturated long or shortchain alk(en)yl, branched chain alk(en)yl and C₅-C₈ cyclic ring systems;

[0240] R² thru' R⁹ may be the same or different and may be independentlyselected from H, straight or branched chain lower alk(en)yl, and C₅-C₈cyclic ring systems;

[0241] n is a number within the range of about 60 to about 120,preferably about 80, and

[0242] X⁻ is preferably acetate, but may instead be for example halide,organic carboxylate, organic sulphonate or the like. Suitable quaternarysilicone polymers of this class are described in EP-A-0 530 974.

[0243] Amino functional silicones suitable for use in shampoos andconditioners of the invention will typically have a mole % aminefunctionality in the range of from about 0.1 to about 8.0 mole %,preferably from about 0.1 to about 5.0 mole most preferably from about0.1 to about 2.0 mole %. In general the amine concentration should notexceed about 8.0 mole % since we have found that too high an amineconcentration can be detrimental to total silicone deposition andtherefore conditioning performance.

[0244] The viscosity of the amino functional silicone is notparticularly critical and can suitably range from about 100 to about500,000 cst.

[0245] Specific examples of amino functional silicones suitable for usein the invention are the aminosilicone oils DC2-8220, DC2-8166,DC2-8466, and DC2-8950-114 (all ex Dow Corning), and GE 1149-75, (exGeneral Electric Silicones).

[0246] Also suitable are emulsions of amino functional silicone oilswith non ionic and/or cationic surfactant.

[0247] Suitably such pre-formed emulsions will have an average aminofunctional silicone droplet size in the shampoo composition of less than30, preferably less than 20, more preferably less than 10 μm. Again, wehave found that reducing the droplet size generally improvesconditioning performance. Most preferably the average amino functionalsilicone droplet size in the composition is less than 2 μm ideally itranges from 0.01 to 1 μm.

[0248] Pre-formed emulsions of amino functional silicone are alsoavailable from suppliers of silicone oils such as Dow Corning andGeneral Electric. Specific examples include DC929 Cationic Emulsion,DC939 Cationic Emulsion, and the non-ionic emulsions DC2-7224, DC2-8467,DC2-8177 and DC2-8154 (all ex Dow Corning).

[0249] An example of a quaternary silicone polymer useful in the presentinvention is the material K3474, ex Goldschmidt.

[0250] For shampoo compositions according to the invention intended forthe treatment of “mixed” hair (i.e. greasy roots and dry ends), it isparticularly preferred to use a combination of amino functional andnon-amino functional silicone in compositions of the invention,especially when these are in the form of shampoo compositions. In such acase, the weight ratio of amino functional silicone to non-aminofunctional silicone will typically range from 1:2 to 1:20, preferably1:3 to 1:20, more preferably 1:3 to 1:8.

[0251] The total amount of silicone incorporated into compositions ofthe invention depends on the level of conditioning desired and thematerial used. A preferred amount is from 0.01 to 10 wt % although theselimits are not absolute. The lower limit is determined by the minimumlevel to achieve conditioning and the upper limit by the maximum levelto avoid making the hair and/or skin unacceptably greasy.

[0252] We have found that a total amount of silicone of from 0.3 to 5,preferably 0.5 to 3 wt % is a suitable level.

[0253] The viscosity of silicones and silicone emulsions can be measuredby means of a glass capillary viscometer as set out further in DowCorning Corporate Test Method CTM004, Jul. 20, 1970.

[0254] In compositions comprising silicone, it is preferred that asuspending agent for the silicone also be present. Suitable suspendingagents are as described hereinabove.

[0255] (ii) Non-silicone Oily Conditioning Components

[0256] Compositions according to the present invention may also comprisea dispersed, non-volatile, water-insoluble oily conditioning agent.

[0257] This component will be dispersed in the composition in the formof droplets, which form a separate, discontinuous phase from theaqueous, continuous phase of the composition. In other words, the oilyconditioning agent will be present in the shampoo composition in theform of an oil-in-water emulsion.

[0258] By “insoluble” is meant that the material is not soluble in water(distilled or equivalent) at a concentration of 0.1% (w/w), at 250° C.

[0259] Suitably, the D_(3,2) average droplet size of the oilyconditioning component is at least 0.4, preferably at least 0.8, andmore preferably at least 1 μm. Additionally, the D_(3,2) average dropletsize of the oily conditioning component is preferably no greater than10, more preferably no greater 8, more preferably no greater than 5, yetmore preferably no greater than 4, and most preferably no greater than3.5 μm.

[0260] The oily conditioning agent may suitably be selected from oily orfatty materials, and mixtures thereof.

[0261] Oily or fatty materials are preferred conditioning agents in theshampoo compositions of the invention for adding shine to the hair andalso enhancing dry combing and dry hair feel.

[0262] Preferred oily and fatty materials will generally have aviscosity of less than 5 Pa.s, more preferably less than 1 Pa.s, andmost preferably less than 0.5 Pa.s, e.g. 0.1 Pa.s and under as measuredat 25° C. with a Brookfield Viscometer (e.g. Brookfield RV) usingspindle 3 operating at 100 rpm.

[0263] Oily and fatty materials with higher viscosities may be used. Forexample, materials with viscosities as high as 65 Pa.s may be used. Theviscosity of such materials (i.e. materials with viscosities of 5 Pa.sand greater) can be measured by means of a glass capillary viscometer asset out further in Dow Corning Corporate Test Method CTM004, Jul. 20,1970.

[0264] Suitable oily or fatty materials are selected from hydrocarbonoils, fatty esters and mixtures thereof.

[0265] Hydrocarbon oils include cyclic hydrocarbons, straight chainaliphatic hydrocarbons (saturated or unsaturated), and branched chainaliphatic hydrocarbons (saturated or unsaturated). Straight chainhydrocarbon oils will preferably contain from about 12 to about 30carbon atoms. Branched chain hydrocarbon oils can and typically maycontain higher numbers of carbon atoms. Also suitable are polymerichydrocarbons of alkenyl monomers, such as C₂-C₆ alkenyl monomers. Thesepolymers can be straight or branched chain polymers. The straight chainpolymers will typically be relatively short in length, having a totalnumber of carbon atoms as described above for straight chainhydrocarbons in general. The branched chain polymers can havesubstantially higher chain length. The number average molecular weightof such materials can vary widely, but will typically be up to about2000, preferably from about 200 to about 1000, more preferably fromabout 300 to about 600.

[0266] Specific examples of suitable hydrocarbon oils include paraffinoil, mineral oil, saturated and unsaturated dodecane, saturated andunsaturated tridecane, saturated and unsaturated tetradecane, saturatedand unsaturated pentadecane, saturated and unsaturated hexadecane, andmixtures thereof. Branched-chain isomers of these compounds, as well asof higher chain length hydrocarbons, can also be used. Exemplarybranched-chain isomers are highly branched saturated or unsaturatedalkanes, such as the permethyl-substituted isomers, e.g., thepermethyl-substituted isomers of hexadecane and eicosane, such as2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and2,2,4,4,6,6-dimethyl-8-methylnonane, sold by Permethyl Corporation. Afurther example of a hydrocarbon polymer is polybutene, such as thecopolymer of isobutylene and butene. A commercially available materialof this type is L-14 polybutene from Amoco Chemical Co. (Chicago, Ill.,U.S.A.).

[0267] Particularly preferred hydrocarbon oils are the various grades ofmineral oils. Mineral oils are clear oily liquids obtained frompetroleum oil, from which waxes have been removed, and the more volatilefractions removed by distillation. The fraction distilling between 250°C. to 300° C. is termed mineral oil, and it consists of a mixture ofhydrocarbons ranging from C₁₆H₃₄ to C₂₁H₄₄. Suitable commerciallyavailable materials of this type include Sirius M85 and Sirius M125, allavailable from Silkolene.

[0268] Suitable fatty esters are characterised by having at least 10carbon atoms, and include esters with hydrocarbyl chains derived fromfatty acids or alcohols, e.g., monocarboxylic acid esters, polyhydricalcohol esters, and di- and tricarboxylic acid esters. The hydrocarbylradicals of the fatty esters hereof can also include or have covalentlybonded thereto other compatible functionalities, such as amides andalkoxy moieties, such as ethoxy or ether linkages.

[0269] Monocarboxylic acid esters include esters of alcohols and/oracids of the formula R′COOR in which R′ and R independently denote alkylor alkenyl radicals and the sum of carbon atoms in R′ and R is at least10, preferably at least 20.

[0270] Specific examples include, for example, alkyl and alkenyl estersof fatty acids having aliphatic chains with from about 10 to about 22carbon atoms, and alkyl and/or alkenyl fatty alcohol carboxylic acidesters having an alkyl and/or alkenyl alcohol-derived aliphatic chainwith about 10 to about 22 carbon atoms, benzoate esters of fattyalcohols having from about 12 to 20 carbon atoms.

[0271] The monocarboxylic acid ester need not necessarily contain atleast one chain with at least 10 carbon atoms, so long as the totalnumber of aliphatic chain carbon atoms is at least 10. Examples includeisopropyl isostearate, hexyl laurate, isohexyl laurate, isohexylpalmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecylstearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate,lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyloleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyladipate.

[0272] Di- and trialkyl and alkenyl esters of carboxylic acids can alsobe used. These include, for example, esters of C₄-C₈ dicarboxylic acidssuch as C₁-C₂₂ esters (preferably C₁-C₆) of succinic acid, glutaricacid, adipic acid, hexanoic acid, heptanoic acid, and octanoic acid.Examples include diisopropyl adipate, diisohexyl adipate, anddiisopropyl sebacate. Other specific examples include isocetyl stearoylstearate, and tristearyl citrate.

[0273] Polyhydric alcohol esters include alkylene glycol esters, forexample ethylene glycol mono and di-fatty acid esters, diethylene glycolmono- and di-fatty acid esters, polyethylene glycol mono- and di-fattyacid esters, propylene glycol mono- and di-fatty acid esters,polypropylene glycol monooleate, polypropylene glycol monostearate,ethoxylated propylene glycol monostearate, polyglycerol poly-fatty acidesters, ethoxylated glyceryl monostearate, 1,3-butylene glycolmonostearate, 1,3-butylene glycol distearate, polyoxyethylene polyolfatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitanfatty acid esters and mono-, di-and triglycerides.

[0274] Particularly preferred fatty esters are mono-, di- andtriglycerides, more specifically the mono-, di-, and triesters ofglycerol and long chain carboxylic acids such as C₁-C₂₂ carboxylicacids. A variety of these types of materials can be obtained fromvegetable and animal fats and oils, such as coconut oil, castor oil,safflower oil, sunflower oil, cottonseed oil, corn oil, olive oil, codliver oil, almond oil, avocado oil, palm oil, sesame oil, peanut oil,lanolin and soybean oil. Synthetic oils include triolein and tristearinglyceryl dilaurate.

[0275] Specific examples of preferred materials include cocoa butter,palm stearin, sunflower oil, soyabean oil and coconut oil.

[0276] The oily or fatty material is suitably present at a level of from0.05 to 10, preferably from 0.2 to 5, more preferably from about 0.5 to3 wt %.

[0277] The compositions of this invention preferably contain no morethan 3 wt % of a styling polymer, more preferably less than 1% of astyling polymer, preferably contain less than 0.1% by weight a stylingpolymer, and optimally are free of styling polymer.

[0278] Adjuvants

[0279] The compositions of the present invention may also containadjuvants suitable for hair care. Generally such ingredients areincluded individually at a level of up to 2, preferably up to 1 wt % ofthe total composition.

[0280] Among suitable hair care adjuvants, are:

[0281] (i) natural hair root nutrients, such as amino acids and sugars.Examples of suitable amino acids include arginine, cysteine, glutamine,glutamic acid, isoleucine, leucine, methionine, serine and valine,and/or precursors and derivatives thereof. The amino acids may be addedsingly, in mixtures, or in the form of peptides, e.g. di- andtripeptides. The amino acids may also be added in the form of a proteinhydrolysate, such as a keratin or collagen hydrolysate. Suitable sugarsare glucose, dextrose and fructose. These may be added singly or in theform of, e.g. fruit extracts. A particularly preferred combination ofnatural hair root nutrients for inclusion in compositions of theinvention is isoleucine and glucose. A particularly preferred amino acidnutrient is arginine.

[0282] (ii) hair fibre benefit agents. Examples are:

[0283] ceramides, for moisturising the fibre and maintaining cuticleintegrity. Ceramides are available by extraction from natural sources,or as synthetic ceramides and pseudoceramides. A preferred ceramide isCeramide II, ex Quest. Mixtures of ceramides may also be suitable, suchas Ceramides LS, ex Laboratoires Serobiologiques.

[0284] The invention will now be further illustrated by the following,non-limiting Examples:

EXAMPLES

[0285] Coated particles comprising solid silica cores and siliconecoating polymer as described in JP 10144622 were used. Two types ofcoated particles emulsions were used, the details of which are asfollows: Coated Particles I Coated Particles II (“CPI”) (“CPII”) Size(nm) about 175 about 115 (nm) Wt ratio 80:20 50:50 core:coating Siliconepolydimethylsiloxane polydimthylsiloxane coating Solid core colloidalsilica colloidal silica Wt % of coated 20 20 particles in emulsionEmulsifying Anionic Anionic surfactant

[0286] The following base conditioner formulations were used: Base A Wt% Cocotrimonium chloride 0.84  Distearyl dimethyl ammonium 0.375chloride Cetostearyl alcohol 3.00  CPI or CRII see below Water, balanceto a 100%

[0287] Base B Wt % PEG-2 oleammonium chloride 2.00 Behentrimoniummethosulphate 1.00 TAS 0.75 Citric acid 0.10 Cetyl alcohol 3.00 Stearylalcohol 2.00 CPI or CPII see below Water, balance to a 100%

[0288] Switch Test

[0289] CPI emulsion was added to the Base A formulation as follows:Composition 1: Control 2 CPI emulsion nil 2.50 (20% active)

[0290] CPI emulsion was added to the Base B formulation as follows: 3Composition Control 4 5 6 7 8 9 10 CPI emulsion nil 2.5 2.5 5.0  5.0 5.02.5 2.5 (20% active) Silicone nil 0.5 0.1 1.25 0.5 0.1 nil nil DC-1786(40% active) Silicone nil nil nil nil nil nil 0.5 0.1 DC2-1387 (40%active)

[0291] Compositions 1 and 2 and compositions 3 to 10 were tested in ahair switch test. In all cases, the compositions according to theinvention beat the control compositions in the generation of hairvolume.

[0292] Panel Test

[0293] CPI and CPII emulsions were added to the Base B formulation asfollows: 3: Composition Control 4 5 CPI emulsion nil nil 2.5 (20%active) CPII emulsion nil 2.5 nil (20% active)

[0294] Compositions 3, 4 and 5 were assessed in a salon half-head paneltest, involving about 50 panellists. In this test, a stylist washed thewhole hair with a standard shampoo. The stylist then applied one testcomposition to half of the head of hair, and either another testcomposition or the control composition to the other half of the head ofhair. The hair was rinsed and the panellist asked to dry their hair asnormal. The panellists were asked to evaluate a series of stylingattributes associated with the body of the dried hair, each attributebeing scored on a sliding numerical scale. Attribute 3 4 5 Total PanelSample Easy off styling 7.10 7.10 7.30 Manageability 6.40 6.80 7.10 Body6.00 6.40 6.50 Fullness 5.70 6.10 6.30 Bounce 5.60 5.60 6.20 Static 2.402.00 1.60 Flat/limp 3.30 3.20 3.00 Volume challenged panellists (i.e.with fine hair) Easy of styling 6.90 7.50 7.80 Manageability 6.10 7.107.70 Body 5.60 6.70 6.60 Fullness 5.40 6.10 6.00 Bounce 5.40 5.60 5.60Static 2.10 1.60 1.70 Flat/limp 3.40 3.20 3.20

[0295] The higher the score, the more prominent the attribute. Thus fornegative attribute such as static, a lower score is preferable. Takingthe results from the total sample of panellists, the compositionscontaining the coated particles, i.e. 4 and 5, won on most attributes,and at worst scored the same, when compared with the control composition3. taking the results from the panellists with fine or“volume-challenged” hair, compositions 4 and 5 won on all attributeswhen compared with the control composition 3.

1. An aqueous conditioner composition comprising i) a cationicsurfactant; ii) a fatty alcohol material; and iii) from 0.01 to 10 wt %coated particles comprising (a) a solid core having a D3,2 averageparticle size in the range from 10 to 700 nm, and (b) a coating ofsilicone polymer covalently bounded to the solid core.
 2. A compositionaccording to claim 1, in which the weight ratio of the solid core to thesilicone coating polymer is in the range from 20:1 to 1:10, preferablyfrom 20:1 to 2:3, more preferably from 20:1 to 1:1.
 3. A compositionaccording to claim 1 or claim 2, in which the solid core comprisesmaterial selected from polymers, alumina, alumin silicate and colloidalmetals.
 4. A composition according to claim 1 or 2, in which the solidcore is a colloidal silica.
 5. A composition according to claim 1, inwhich the solid core particles have a Youngs Modulus of more than 0.01GPa.
 6. A composition according to claim 1, in which the siliconepolymer is a polyorganosiloxane.
 7. A method of imparting body to haircomprising the following steps i) selecting a conditioner according toclaim 1 ii) applying the conditioner to hair.